MXPA01013283A

MXPA01013283A - Cleaning compositions.

Info

Publication number: MXPA01013283A
Application number: MXPA01013283A
Authority: MX
Inventors: Edward Sherry Alan
Original assignee: Procter & Gamble
Priority date: 1999-06-15
Filing date: 1999-11-03
Publication date: 2002-06-04
Also published as: EP1185604A1; WO2000077143A1; JP2003524681A; CA2374534A1; AR021446A1; ZA200109900B; AU1465600A; AU4684499A; WO2000077144A1

Abstract

The present invention relates to cleaning compositions comprising a surface substantive polymer for cleaning surfaces, particularly the exterior surfaces of a vehicle.

Description

CLEANING COMPOSITIONS TECHNICAL FIELD The present invention relates to the technical field of surface cleaning compositions, especially ceramics, steel, plastic, glass and / or painted surfaces, and to processes for cleaning said surfaces.

BACKGROUND OF THE INVENTION Hard surface cleaning products are widely available in the market. These products are used for two purposes; the first, clean dirt from the surface, and the second leave the surface with an aesthetically pleasing finish, for example stain-free or glossy. However, the products available in the market often require rinsing with water after use. Typically, when water dries on the surface there are water marks, gouges or spots. It is believed that these watermarks are due to the evaporation of water on the surface, which leaves mineral deposits that are present as dissolved solids in the water, for example, calcium or magnesium and salts thereof; or they can be deposits of dirt carried by the water, or even remnants of a cleaning product, for example soap scum.

This problem is frequently exacerbated by some cleaning compositions that modify the surface during the cleaning process, such that after rinsing, the water forms droplets or discrete points on the surface, instead of dripping. These droplets or spots are dried to leave marks or marks perceptible to the consumer, known as watermarks. This problem is particularly evident when cleaning ceramics, steel, plastic, glass or painted surfaces. One means of solving this problem, known in the art, is to dry the water on the surface using a cloth or chamois before the watermarks are formed. However, this drying operation is time consuming and requires considerable physical effort. In US 5 759 980 (Blue Coral) a composition for cleaning cars is described, which eliminates the problem of watermarks. The composition described comprises a surfactant package comprising a silicone-based surfactant and a polymer that is capable of binding to the surface to render it hydrophobic. However, applicants have found that the polymers described herein are removed from the surface during the rinsing of the surface product. Therefore, since it is stated that the hydrophilicity of the surface is provided by the composition described in the patent, and the composition is completely removed from the surface after the first rinse, the intended hydrophilicity is also eliminated. The result is that the benefit provided by the composition is lost when the surface is rinsed.

DE-A-21 61 591 also describes a composition for cleaning cars, wherein the surface is rendered hydrophilic by application of copolymers containing an amino group, such as polymeric ethylene imines, dimethylaminoethyl acrylate or polymeric methacrylate or mixed polymerized. However, as with the aforementioned composition, the polymers are also washed out in the first rinse of the car, thus eliminating any benefit that the polymers could give. In this way, the object of the present invention is to provide a cleaning composition that not only prevents the appearance of watermarks directly after cleaning, but also prevents the formation of watermarks after the first rinse and after subsequent rinses. The compositions of the present invention are applied to the surface, optionally rinsed and allowed to dry. The compositions described herein are specifically designed so that the surface does not require artificial drying, but can be left to dry naturally by evaporation or other suitable mechanism. In addition, the above benefit provided by the composition of the present invention is durable, which means that the benefit can be perceived even after successive rinses, including after intentional rinsing by a user, or with rainwater. Intentional rinsing means rinsing the surface using a suitable rinsing device such as a hose, shower, bucket, cloth, sponge. In addition to the above, an additional problem associated with such cleaning compositions is that they require the user to rub or scrub the surface, which also consumes time and requires physical effort. Therefore, a secondary object of the present invention is to provide a cleaning composition that not only provides a benefit of not drying, but also does not require the user to scrub or scrub the surface to be cleaned. The term "surface" means those surfaces regularly found in houses, such as kitchens and bathrooms, for example floors, walls, tiles, windows, sinks, bathrooms, showers, toilets, accessories and furniture made of different materials such as ceramics, porcelain, varnish, vinyl, non-waxy vinyl, linoleum, melamine, glass, any plastic, laminated wood, metal, especially steel and chrome, varnished or sealed surfaces and the exterior surfaces of a vehicle, for example painted plastic or glass surfaces and finishing coatings.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a cleaning composition suitable for cleaning a surface, comprising a substantive surface polymer wherein said polymer is capable of modifying the surface to make it hydrophilic, providing a contact angle between the water and the surface of less than fifty. In another aspect, the present invention relates to a cleaning composition suitable for cleaning a surface, comprising a substantive surface polymer, wherein said polymer is capable of lastingly modifying the surface, to make it hydrophilic, providing a contact angle between. the water and the surface of less than 50 °.

DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention requires a substantive surface polymer as an essential component of the composition.

Surface substantive polymer The composition of the present invention comprises a substantive surface polymer as an essential component thereof. By substantive surface polymer is meant a polymer that is capable of modifying the surface, adhering or associating in some way with the surface to be cleaned, in such a way that it remains on the surface during and after the cleaning operation. Said adhesion or association can be, for example, by means of covalent interaction; electrostatic interaction; hydrogen bonding; or through Van der Waals forces. The polymer modifies the surface making it hydrophilic, which means that the contact angle between the water and the surface, after having been treated with the composition containing the polymer, is less than 50 °, preferably less than 40 °, preferably less than 30 °, most preferably less than 20 ° or less. The contact angle is measured according to the American Standard Test Method for measuring the contact angle, designation number D5725-95, using the devices sold under the name Contact Angle Measuring System G10, from Kruss. In another aspect of the present invention, the polymer is capable of lastingly modifying the surface by making it hydrophilic, providing a contact angle between water and the surface of less than 50 °, preferably less than 40 °, preferably less than 30 °, very preferably less than 20 ° or less. By "durably" it is meant that the hydrophilic modification of the surface is maintained at least during one rinse, preferably at least three rinses, preferably at least five rinses, preferably at least seven rinses, preferably at least ten rinses , or even at least thirty rinses, carried out according to the rinsing test method described herein.

Rinse test method The rinse test method used in accordance with the present invention, consists of spraying the surface with water having 24 degrees of French hardness, using a water supply device, for example a conventional garden hose or a shower head, at a distance of 1.0 meter surface for 30 seconds. The water flow rate of the water supply system is approximately 10 liters per minute. The polymer of the present invention may be a homo- or copolymer, and preferably comprises at least one hydrophobic or cationic portion and at least one hydrophilic portion. The hydrophobic portion is preferably a linear or branched aromatic carbon chain of C8-18, vinylimidazole or a propoxy group. The cationic moieties include any group that is positively charged or has a positive dipole. The hydrophilic portion may be selected from any portion that forms a dipole that is capable of hydrogen bonding. Suitable examples of said hydrophilic moieties include vinylpyrrolidone, carboxylic acid such as acrylic acid, methacrylic acid, maleic acid and ethoxy groups. In a preferred aspect of the present invention, the polymer is selected from the group consisting of polyvinylpyrrolidone copolymers. A particularly preferred polyvinylpyrrolidone copolymer is that of the polymers N-vinylimidazole-N-vinylpyrrolidone (PVPVI), available for example from BASF under the trademarks Luvitec VP155K18P. Preferred PVPVI polymers have an average molecular weight of 1,000 to 5,000,000, preferably 5,000 to 2,000,000, preferably 5,000 to 500,000, and most preferably 5,000 to 15,000. Preferred PVPVI polymers comprise at least 55%, preferably at least 60%, of N-vinylimidazole monomers. Alternatively, another suitable polymer may be a quaternized PVPVI, for example the compound sold under the trademark Luvitec Quat 73W from BASF. Other suitable copolymers of vinyl pyrrolidone for use in the compositions of the present invention are quaternized copolymers of vinyl pyrrolidone / acrylate or dialkylaminoalkyl methacrylate. The quaternized copolymers of vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate suitable for use in the compositions of the present invention are according to the following formula: wherein n is between 20 and 99, and preferably between 40 and 90 mole% and m is between 1 and 80, and preferably between 5 and 40 mole%; R-i represents H or CH 3; and denotes 0 or 1; R2 is -CH2-CHOH-CH2- or CxH =. where x = 2 to 18; R3 represents a lower alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl, or R4 denotes a lower alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl; X "is selected from the group consisting of Cl, Br, I, 1 / 2S0, HSO4 and CH3S03 The polymers can be prepared by the process described in French Patent Nos. 2,077,143 and 2,393,573 The quaternized copolymers of vinylpyrrolidone / acrylate or Preferred dialkylaminoalkyl methacrylate for use herein have a molecular weight of between 1,000 and 1,000,000, preferably between 10,000 and 500,000, and preferably between 10,000 and 100,000.The said copolymers of vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate are commercially available under the brand Copolymer 845®, Gafquat 734® or Gafquat 755® from ISP Corporation, New York, New York and Montreal, Canada, or from BASF under the brand name Luviquat®. Quaternized copolymers of vinylpyrrolidone and dimethyl aminoethylmethacrylate are most preferred ( Polyquaternium 11), available from BASF Another preferred polymer is the polyvinylpyridine N-oxide polymer (PVNO) available for example from R eilly The preferred PVNO polymers have an average molecular weight of from 1,000 to 200,000, preferably from 5,000 to 500,000, preferably from 15,000 to 500,000.

The average molecular weight scale was determined by light scattering, as described by Barth H.G. and Mays J.W., in Chemical Analysis Vol. 113, "Modern Methods of Polymer Characterization." Preferably, the polymer is present in the composition at a level from 0.001% to 10%, preferably from 0.01% to 5%, preferably from 0.01% to 1% by weight of the composition.

Optional ingredients The compositions according to the present invention may comprise a variety of optional ingredients depending on the technical benefit required and the treated surface. Optional ingredients suitable for use herein may be selected from the groups consisting of anti-re-fouling ingredients, surfactants, chelating agents, enzymes, hydrotrope ions, foam control agents, solvents, buffers, thickening agents, radical scavengers, polymers of suspension of dirt, pigments, dyes, preservatives and / or perfumes.

Ingredients against re-fouling In a preferred embodiment, the compositions according to the present invention comprise an anti-re-fouling ingredient or a mixture thereof.

Suitable anti-renmination agents include those well known to those skilled in the art, which include polyalkoxylene glycol diester, vinylpyrrolidone homopolymer or copolymer, other than those described above, polysaccharide polymer, polyalkoxylene glycol, mono- or diblocked polyalkoxylene glycol, as defined herein below, or a mixture thereof. Typically, the compositions of the present invention may comprise up to 20%, preferably from 0.001% to 10%, preferably from 0.005% to 5%, and preferably from 0.005% to 2% by weight of an anti-re-fouling ingredient. The vinylpyrrolidone homopolymers suitable for use herein are the homopolymers of N-vinylpyrrolidone having the following repeating monomer: wherein n (degree of polymerization) is an integer of 10 to 1,000,000, preferably 20 to 100,000, and preferably 20 to 10,000. Accordingly, the vinylpyrrolidone homopolymers ("PVP") suitable for use herein have an average molecular weight of from 1,000 to 100,000,000, preferably from 2,000 to 10,000,000, preferably from 5,000 to 1,000,000, and most preferably from 50,000 to 500,000. Suitable vinylpyrrolidone homopolymers are commercially available from ISP Corporation, New York, New York, and Montreal, Canada, under the brands PVP K-15® (molecular weight of viscosity of 10,000), PVP K-30® (average molecular weight of 40,000), PVP K-60® (molecular weight average of 160,000), and PVP K-90® (average molecular weight of 360,000). Other suitable vinylpyrrolidone homopolymers which are commercially available from BASF Corporation include Sokalan HP 165® and Sokalan HP 12®, vinylpyrrolidone homopolymers known to those skilled in the detergent field (see for example EP-A-262,897 and EP-A- 256,696). Vinylpyrrolidone copolymers suitable for use herein include copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers or mixtures thereof. The alkylenically unsaturated monomers of the copolymers herein include unsaturated dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid and vinyl acetate. Any of the anhydrides of the unsaturated acids can be used, for example acrylate, methacrylate. Aromatic monomers such as styrene, sulfonated styrene, alpha-methyl-styrene, vinyltoluene, t-butyl-styrene and similar well-known monomers can be used.

The molecular weight of the vinylpyrrolidone copolymer is not especially critical as long as the copolymer is water-soluble, has some surface activity and is adsorbed on the hard surface of the liquid composition or solution (ie, under dilution conditions in use) comprising it, in such a way that it increases the hydrophilicity of the surface. However, preferred copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers or mixtures thereof, have a molecular weight of between 1,000 and 1,000,000, preferably between 10,000 and 500,000, and preferably between 10,000 and 200,000. Said copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers, such as the PVP / vinyl acetate copolymers, are commercially available under the commercial series Luviskol® from BASF. Other polymers suitable for use herein are polysaccharide polymers including substituted cellulose materials such as carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, succinoglycan, and natural polysaccharide polymers such as xanthan gum, guar gum, locust bean gum, tragacanth gum or derivatives thereof and their mixtures. Particularly, polysaccharide polymers to be used herein are xanthan gum and derivatives thereof. Xanthan gum and its derivatives may be commercially available for example from Kelco under the trademarks Keltrol RD®, Kelzan S® or Kelzan T®.

Additional anti-re-fouling ingredients, suitable for use herein, include polyalkoxylene glycol, mono- or di-blocked poly-xylene glycol or a mixture thereof, as defined herein below. The polyalkoxylene glycols suitable for use herein are according to the following formula, H-0- (CH2-CHR2?) N-H. The monoblocked polyalkoxylene glycols suitable for use herein are according to the following formula, R -? - O- (CH2-CHR20) n-H. Diblocked polyalkoxylene glycols suitable for use herein are according to the following formula, R? -O- (CH2-CHR2O) n -R3. In these formulas, the substituents Ri and R3 are linear or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains, having 1 to 30 carbon atoms, or substituted or unsubstituted hydrocarbon chains, linear or branched, which they have from 1 to 30 carbon atoms and carry an amino group, R2 is hydrogen or a straight or branched hydrocarbon chain having from 1 to 30 carbon atoms, and n is an integer greater than 0. Preferably R1 and R3 are groups alkyl, alkenyl or aryl substituted or unsubstituted, linear or branched, having 1 to 30 carbon atoms, preferably 1 to 16, preferably 1 to 8, and most preferably 1 to 4; or linear or branched alkyl, alkenyl or aryl groups, substituted or unsubstituted, bearing an amino group and having from 1 to 30 carbon atoms, preferably from 1 to 16, preferably from 1 to 8, and most preferably from 1 a 4. Preferably R2 is hydrogen or a linear or branched alkyl, alkenyl or aryl group having 1 to 30 carbon atoms, preferably 1 to 16, preferably 1 to 8, and most preferably R2 is methyl or hydrogen. Preferably, n is an integer greater than 1, preferably from 5 to 1000, preferably from 10 to 100, preferably from 20 to 60, and most preferably from 30 to 50. Preferred mono- and di-block polyalkoxylene glycols, polyalkoxylene glycols for use herein, they have a molecular weight of at least 200, preferably from 400 to 5000 and preferably from 800 to 3000. Monoblocked polyalkoxylene glycols suitable for use herein include 2-aminopropylpolyethylene glycol (MW 2000), methylpolyethylene glycol (MW 1800) and the like. Said monoblocked polyalkoxylene glycols can be commercially available from Hoechst under the polyglycol series, or from Hunstman under the trademark XTJ®. Suitable polyalkoxylene glycols for use herein are polyethylene glycols such as polyethylene glycol (MW 2000). Diblocked polyalkoxylene glycols suitable for use herein include O, O'-bis (2-aminopropyl) polyethylene glycol (MW 2000), O, O'-bis (2-aminopropyl) polyethylene glycol (MW 400), O, O'-dimethyl-polyethylene glycol (MW 2000), dimethyl polyethylene glycol (MW 2000) ) or mixtures thereof. A preferred diblocked polyalkoxylene glycol for use herein is dimethylpolyethylene glycol (MW 2000). For example, Hoechst dimethylpolyethylene glycol may be commercially available as the polyglycol series, for example PEG DME-2000, or from Huntsman under the names Jeffamine® and XTJ®.

Preferred anti-renmination agents include oligomeric terephthalate esters, typically prepared by methods that include at least one transesterification / oligomerization, often with a metal catalyst such as titanium (IV) alkoxide. Such esters can be prepared by using additional monomers that can be incorporated into the ester structure by one, two, three, four or more positions, of course without forming a densely intertwined general structure. Suitable anti-renmination agents include a sulphonated product of a substantially linear ester oligomer, comprised of an oligomeric ester backbone of terephthaloyl and oxyalkylenoxy repeat units, and sulfonated terminal portions derived from allyl covalently attached to the backbone, for example as described in the US patent No. 4,968,451, November 6, 1990, for J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared (a) by ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisuphyte in water. Other anti-re-fouling agents include the polyoxyethylene 1, 2-propylene / blocked end polyoxyethylene terephthalate polyesters of the U.S.A. No. 4,711, 730, December 8, 1987, for Gosselink et al., For example, those produced by transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of anti-re-fouling agents include: the partially and fully blocked anionic oligomeric esters of the U.S. patent. No. 4,721, 580, January 26, 1988, for Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the blocked nonionic polyester oiigomeric compounds of the U.S.A. No. 4,702,857, October 27, 1987, for Gosselink, for example produced from DMT, PEG blocked with methyl (Me) and EG and / or PG; or a combination of DMT, EG and / or PG, PEG-Me-blocked and Na-dimethyl-5-sulfoisophthalate; and the anionic esters of blocked end terephthalate, especially sulfoaroyl, of the U.S. patent. No. 4,877,896, October 31, 1989, for Maldonado, Gosselink and others; an example is an ester composition made from the monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably comprising PEG, for example PEG 3400. Anti-re-fouling agents also include: simple copolymer blocks of ethylene terephthalate or terephthalate propylene with polyethylene oxide or polypropylene oxide terephthalate; see the patent of E.U.A. No. 3,959,230, for Hays, May 25, 1976, and the patent of E.U.A. No. 3,893,929, for Basadur, July 8, 1975; cellulose derivatives such as the hydroxyethyl cellulose polymers available as METHOCEL from Dow; the C? -C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. Pat. No. 4,000,093, December 28, 1976, for Nicol et al .; and the methylcellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit of from about 1.6 to about 2.3, and a solution viscosity of about 80 to about 120 centipoise, measured at 20 ° C as an aqueous solution at 2 ° C. %. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are brands of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Suitable anti-re-fouling agents characterized by hydrophobic poly (vinyl ester) segments include poly (vinyl ester) graft copolymers, for example vinyl esters Ci-Cß, preferably poly (vinyl acetate) grafted onto polyalkylene oxide backbones. See European patent application 0 219 048, published on April 22, 1987, by Kud and others. Commercially available examples include SOKALAN anti-redenution agents such as SOKALAN HP-22, available from BASF, Germany. Anti-re-fouling agents are polyesters with repeating units containing 10-15% by weight of ethylene terephthalate, together with 80-90% by weight of polyoxyethylene terephthalate derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. Another preferred anti-renmination agent is an oligomer having the empirical formula (CAP) 2 (EG / PG) 5 (T) 5 (SIP) ?, which comprises units of terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and ox -1, 2-propylene (EG / PG), which ends preferably with end blocks (CAP), preferably modified isethionates, as in an oligomer comprising a sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy units and oxy- 1,2-propyleneoxy in a defined ratio, preferably from about 0.5: 1 to about 10: 1, and two end block units derived from sodium 2- (2-hydroxyethoxy) ethane sulfonate. Said anti-re-fouling agent also preferably comprises from 0.5% to 20% by weight of the oligomer, of a crystallinity-reducing stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate, or a member selected from xylene-, eumeno- and toluenesulfonates, or mixtures thereof; these stabilizers or modifiers being introduced into the synthesis vessel, as taught in the US patent. No. 5,415,807 to Gosselink, Pan, Kellet and Hall, issued May 16, 1995. Suitable monomers for the anti-renin-like agent above include Na-2- (2-hydroxyethoxy) ethanesulfonate, DMT, Na-dimethyl-5- sulfoisophthalate, EG and PG. Another group of anti-re-fouling agents are the oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxysulfonates, a unit that is at least trifunctional by way of which ester bonds are formed by producing a branched oligomer skeleton, and combinations thereof; (b) at least one non-sulfonated unit which is a 1,2-oxyalkylenoxy portion; and (2) one or more blocking units selected from non-ionic blocking units, anionic blocking units such as alkoxylated, preferably ethoxylated isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives, and mixtures thereof. The esters of the empirical formula are preferred:. { (CAP) x (EG / PG) y '(DEG) y "(PEG) y'" (T) z (SIP) z '(SEG) q (B) m} where CAP, EG / PG, PEG, T and SIP are as mentioned above, (DEG) represents units di (oxyethylene) oxy, (SEG) represents units derived from the sulfoethyl ether of glycerin and related units, (B) represents units of branching which are at least trifunctional, whereby ester bonds are formed by producing a branched oligomer skeleton, x is from about 1 to about 12, and 'is from about 0.5 to about 25, and' is from 0 to about 12, and '"is from 0 to about 10, and' + and" + and "" add from about 0.5 to about 25, z is from about 1.5 to about 25, z 'is from 0 to about 12; z + z 'amount to about 1.5 to about 25, which is from about 0.05 to about 12; m is from about 0.01 to about 10, and x, y ', y ", y'", z, z ', q and m represent the average number of moles of the corresponding units per mole of said ester, and said ester has a molecular weight which varies from approximately 500 to approximately 5,000. Preferred SEG and CAP monomers for the above esters include Na-2- (2,3-dihydroxypropoxy) ethanesulfonate ("SEG"), Na-2-. { 2- (2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and its homologues and mixtures, and the products of ethoxylation and sulphonation of allylic alcohol. Preferred anti-re-fouling agent esters in this class include the transesterification and oligomerization product of 2-. { 2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and / or 2- [2-. { 2- (2-hydroxy-ethoxy) ethoxy} sodium ethoxy] -ethansulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate, EG, and PG, using an appropriate Ti (IV) catalyst, and can be designated as (CAP) 2 (T) 5 (EG / PG) 1.4 (SEG) 2.5 (B) 0.13, where CAP is (Na + O3S [CH2CH2?] 3.5) - and B is a glycerin unit and the EG / PG molar ratio is approximately 1.7: 1 , determined by conventional gas chromatography after complete hydrolysis. Additional classes of anti-re-fouling agents include (I) non-ionic terephthalates, using diisocyanate coupling agents to link polymeric ester structures, see for example the U.S. No. 4,201, 824 of Violland et al., And the patent of E.U.A. No. 4,240,918 to Lagasse et al .; and (II) anti-re-fouling agents with carboxylate end groups, prepared by adding trimellitic anhydride to known anti-renmination agents to convert terminal hydroxyl groups into trimellitate esters. With the appropriate selection of catalyst, the trimellitic anhydride forms linkages with the ends of the polymer through a carboxylic acid ester isolated from trimellitic anhydride in place of the opening of the anhydride linkage. Nonionic or anionic anti-resorption agents can be used as starting materials, provided they have terminal hydroxyl groups that can be esterified. See, for example, the patent of E.U.A. No. 4,525,524 of Tung et al. Other classes include: (lll) anionic anti-re-fouling agents based on terephthalate of the urethane-bound variety; see the patent of E.U.A. No. 4,201, 824 of Violland et al .; (IV) copolymers of poly (vinylcaprolactam) and related copolymers, with monomers such as vinylpyrrolidone and / or dimethylaminoethylmethacrylate, including nonionic and cationic polymers, see U.S. No. 4,579,681 to Rupert et al .; (V) graft copolymers, in addition to those of SOKALAN type, of BASF, made by grafting acrylic monomers onto sulfonated polyesters. It is stated that these anti-re-fouling agents have dirt removal and anti-redeposition activity similar to that of the known cellulose ethers, see EP 279,134 A, 1988, for Rhone-Poulenc Chemie. Another class includes (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate, on proteins such as caseins, see EP 457,205 A for BASF (1991); and (VII) polyester anti-re-fouling agents prepared by condensation of adipic acid, caprolactam and polyethylene glycol, see Bevan et al., DE 2,335,044 for Unilever N.V., 1974. Other anti-re-fouling agents are described in US Patents. Nos. 4,240,918, 4,787,989 and 4,525,524. Other suitable anti-re-fouling agents include the hydrophobically modified cellulosic polymers. The cellulosic polymer to be used herein is preferably of the following formula: wherein each R is selected from the group consisting of R2, Rc wherein: - • each R2 is independently selected from the group consisting of H and C1-C4 alkyl; each Rc is Q II - (CH2) y- C-OZj wherein each Z is independently selected from the group consisting of M, R2) Rc and RH; each RH is independently selected from the group consisting of C5-C20 alkyl, Cs-C7 cycloalkyl, C -C2o alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (C-? - C2o) -2- alkoxy hydroxyalkyl, alkylaryloxy (C -C2o) -2-hydroxyalkyl, (R4) 2N-alkyl, (R ^ N-2-hydroxyalkyl, (R4) 3N-alkyl, (R) 3N-2-hydroxyalkyl, aryloxy (C6-Ci2 ) -2-hydroxyalkyl, each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl, and hydroxyalkyl; each R5 is independently selected from the group consisting of H, C1-C20 alkyl. C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4) 2N-alkyl and (R4) 3N-alkyl; wherein M is an appropriate cation selected from the group consisting of Na, K, V2 Ca and Y2 Mg; each x is from 0 to about 5; each y is from about 1 to about 5; and with the proviso that: the degree of substitution for the RH group is between approximately 0.001 and 0.1, preferably between approximately 0.005 and 0.05, preferably between approximately 0.01 and 0.05; the Degree of substitution for the group Rc where Z is H or M, is between approximately 0.2 and 2.0, preferably between approximately 0.3 and 1.0, preferably between approximately 0.4 and 0.7; if any RH carries a positive charge, it is balanced with a suitable anion; and two R 4 on the same nitrogen can form a ring structure selected from the group consisting of piperidine and morpholine. The "Degree of substitution" for the RH group, which is sometimes abbreviated here as "DSRH", means the number of moles of RH components of the group that are substituted per unit of anhydrous glucose, wherein one unit of anhydrous glucose is a Six-member ring as shown in the repetition unit of the general structure above. The "Degree of substitution" for group Rc, which is sometimes abbreviated here as "DSRC", means the number of moles of Rc components of the group, where Z is H or M, which are substituted per unit of anhydrous glucose, wherein an anhydrous glucose unit is a six-membered ring as shown in the repetition unit of the overhead structure. The requirement that Z be H or M is necessary to ensure that there is a sufficient number of carboxymethyl groups for the resulting polymer to be soluble. It is understood that in addition to the required number of Rc components where Z is H or M, there may be, and preferably are, additional Rc components, where Z is a different group of H or M.

These polymers can be obtained for example using methods such as those described in co-pending applications PCT / US98 / 19139 and PCT / US98 / 19142.

Surfactants An optional preferred component of the compositions described herein is a surfactant. It has been found that the presence of a surfactant in the compositions of the present invention not only improves the cleaning action, but also acts synergistically with the substantive surface polymer. The surfactant can be selected from the group consisting of nonionic, anionic, cationic, zwitterionic and / or amphoteric surfactants. Suitable anionic surfactants for use in the compositions herein include salts or water-soluble acids of the formula ROSO3M, wherein R is preferably a C7-C2 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C7-C24 alkyl component, preferably an alkyl or hydroxyalkyl of C12-C-18, and M is H or a cation, for example, an alkali metal cation (for example sodium, potassium, lithium), or ammonium or substituted ammonium (for example cations of methyl-, dimethyl- and trimethylammonium, quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like).

Other suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO (A) mSO3M, wherein R is a C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably alkyl or hydroxyalkyl of C12-C20, preferably alkyl or hydroxyalkyl of Ci2-C-? 8; A is an ethoxy or propoxy unit; m is greater than zero, usually between about 0.5 and about 6, preferably between about 0.5 about 3; and M is H or a cation which may be, for example, a metal cation (for example, sodium, potassium, lithium, calcium, magnesium, etc.), or an ammonium or substituted ammonium cation. Ethoxylated alkyl sulphates and propoxylated alkyl sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium, and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like. Exemplary surfactants are polyethoxylate (1.0) of C12-C18 alkyl sulfate, (E (1.0) M Ci2-C18), polyethoxylate (2.25) of C12-C18 alkyl sulfate, (E (2.25) MC? 2-C18), polyethoxylate (3.0) of C? 2-C? 8 alkyl sulfate, (E (3.0) M C12-C? 8), and polyethoxylate (4.0) of Ci2-C-? 8 alkyl sulfate, (E (4.0) M C- i2-C-? 8), wherein M is conveniently selected from sodium and potassium. Other particularly suitable anionic surfactants for use herein are the aminosulfonates, which include salts or water-soluble acids of the formula RSO3M, wherein R is a linear or branched, saturated or unsaturated alkyl group of C6-C22, preferably a C-alkyl group. ? 0-C? 6, and preferably a C12-C16 alkyl group, and M is H or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium (for example methyl-, dimethyl- and trimethylammonium cations, quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Alkylarylsulfonates suitable for use herein include salts or water-soluble acids of the formula RSO3M, wherein R is an aryl group, preferably benzyl, substituted with a linear or branched, saturated or unsaturated alkyl group of C6-C22, preferably an alkyl group of C-? oC? 8, and preferably a C12-C16 alkyl group, and M is H or a cation, for example an alkali metal cation (for example, sodium, potassium, lithium, calcium, magnesium, etc.) or ammonium or substituted ammonium (e.g. methyl-, dimethyl- and trimethylammonium cations, quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof , and similar). The alkylsulfonates and alkylarylsulfonates for use herein include primary and secondary alkylsulfonates and primary and secondary alkylarylsulfonates. By "secondary Ce-C22 alkyl sulfonates or secondary C6-C22 alkylarylsulfonates" it is understood that in the formula defined above the SO3M or aryl-SOsM group is bonded to a carbon atom of the alkyl chain placed between two other carbons of carbon. said alkyl chain (secondary carbon atom). For example, the C 14 -C 16 alkylsulfonate salt is commercially available under the name Hostapur ® SAS from Hoechst, and the sodium salt of C 8 alkylsulfonate is commercially available under the name Witconate ÑAS 8 ® from Witco SA. An example of commercially available alkylarylsulfonate is Lauryl arisulfonate from Su.Ma. Particularly preferred alkyl aryl sulphonates are alkyl benzene sulfonate, commercially available under the trademark Nansa®, available from Albrigt &Wilson. Other anionic surfactants useful for detersive purposes can also be used here. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of soap, C3-C24 olefinsulfonates, sulfonated polycarboxylic acprepared by sulfonation of the pyrolyzed product of metal citrates alkaline earth, for example, as described in the British patent specification No. 1, 082,179; alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); Alkylethersulfonates such as Cu-6 methylstersulfonates; acyl glycerol sulfonates, fatty oleilglicerolsulfatos, alkylphenol ethylene oxide, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl and sulfosucclnatos, monoesters of sulfosuccinate (especially monoesters of C12-C18 saturated and unsaturated) and diesters of sulfosuccinate (especially diesters C5-C14 saturated and unsaturated), ethoxylated sulfosuccinates, alkylpolyacharide sulfates such as alkylpolyglucoside sulfates (non-sulphonated non-ionic compounds are described below), branched primary alkyl sulphates, alkylpolyethoxycarboxylates such as those of the formula RO (CH2CH2?) k- CH2COO "M +, wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and resin acids and hydrogenated resin acids are also suitable. as rosin, hydrogenated rosin and acids of. colophony, and hydrophilic rosin acids enados present in, or derived from, tallow tree oil. Additional examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in the U.S. patent. No. 3,929,678, issued December 30, 1975 to Laughiin et al., In column 23, line 58 to column 29, line 23 (incorporated herein by reference). Other anionic surfactants particularly suitable for use herein are alkylcarboxylates and alkylalkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain, preferably from 8 to 18, and preferably from 8 to 16, wherein the alkoxy is propoxy and / or ethoxy, and is preferably ethoxy at a degree of alkoxylation of 0.5 to 20, preferably 5 to 15. The preferred alkylalkoxycarboxylate for use herein is sodium laureth-11-carboxylate (i.e., RO (C2H4O)? or -CH2COONa, with R = Ci2-Cu), commercially available under the trademark Akyposoft® 100NV from Kao Chemical Gbmh. Suitable amphoteric surfactants for use herein include amine oxides having the following formula R 1 R 2 R 3 NO, wherein each of Ri, R 2 and R 3 is independently a straight or branched, substituted or unsubstituted saturated hydrocarbon chain, of 1 to 30 carbon atoms. carbon. Preferred amine oxide surfactants for use in accordance with the present invention are the amine oxides having the following formula R ^ RsNO, wherein R 1 is a hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, preferably from 8 to 16, preferably from 8 to 12, and wherein R2 and R3 are linear or branched, independently substituted or unsubstituted alkyl chains, comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and preferably they are methyl groups. R1 can be a saturated or substituted hydrocarbon chain, linear or branched. Suitable amine oxides for use herein are, for example, natural mixture of C8-C amine oxides, as well as C2-Ci6 amine oxides commercially available from Hoechst. Zwitterionic surfactants for use herein contain a cationic hydrophilic group, for example a quaternary ammonium group, and an anionic hydrophilic group on the same molecule, at a relatively broad pH scale. The typical anionic hydrophilic are carboxylates and sulfonates, although other groups such as sulfates, phosphonates and the like can be used. A generic formula for the zwitterionic surfactants used herein is: wherein Ri is a hydrophobic group; R2 is hydrogen, alkyl or hydroxyalkyl of C-i-Cβ or another substituted alkyl group of C-i-Cβ; R3 is C 1 -C β alkyl or hydroxyalkyl, which may also be attached to R 2 to form ring structures with N, or a C 1 -C 5 carboxylic acid group OR a C 1 -C β sulfonate group; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic group, and is regularly an alkylene, hydroxyalkylene or polyalkoxy group containing from 1 to 10 carbon atoms; and X is a hydrophilic group, which is a carboxylate or sulfonate group. Preferred hydrophobic R1 groups are aliphatic or aromatic hydrocarbon chains, saturated or unsaturated, substituted or unsubstituted, containing linking groups such as amido groups and ester groups. It is preferred that R1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18, and most preferably from 10 to 16. These simple alkyl groups are preferred for reasons of cost and stability. However, the hydrophobic group R1 can also be an amido radical of the formula Ra-C (O) -NH- (C (Rb) 2) m, where Ra is an aliphatic or aromatic hydrocarbon chain, saturated or unsaturated, substituted or unsubstituted, preferably an alkyl group containing from 8 to 20 carbon atoms, preferably up to 18, preferably up to 16, Rb is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, preferably 3, with no more than one hydroxy group in any portion (C (Rb) 2) - The preferred R 2 is hydrogen or a C 1 -C 3 alkyl, most preferably methyl. The preferred R3 is a C1-C4 carboxylic acid group or a C1-C4 sulfonate group, or a C1-C3 alkyl group, and preferably methyl. The preferred R4 is (CH2) n, where n is an integer of 1 to 10, preferably from 1 to 6, preferably from 1 to 3. Some common examples of betaine / sulfobetaine are described in the U.S. Patents. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference. Examples of particularly suitable alkyldimethylbetaines include cocodimethylbetaine, lauryldimethylbetaine, decyl dimethylbetaine, 2- (N-decyl-N, N-dimethyl-ammonia) acetate, 2- (N-coco-N, N-dimethylammonium) acetate, myristyldimethylbetaine, palmityldimethylbetaine, cetyldimethylbetaine, stearyl-dimethylbetaine. For example, Seppic cocodimethylbetaine is commercially available under the trademark Amonyl 265®. Albright & laurylbetaine is commercially available. Wilson under the Empigen BB / L® brand. Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropylbetaine or acylamidopropylene (hydropropylene) sulfobetaine C? O-C fat? . For example, acylamidopropylene (hydropropylene) sulfobetaine Cure-C fat from Sherex is commercially available Company under the brand "Varion CAS® sulfobetaine".

A further example of betaine is lauryl imino dipropionate, commercially available from Rhone-Poulenc under the Mirataine brand H2C-HA ®. Cationic surfactants suitable for use herein include derivatives of quaternary ammonium, phosphonium, imidazolium and sulfonium compounds. Preferred cationic surfactants for use herein are the quaternary ammonium compounds wherein one or two of the hydrocarbon groups bonded to the nitrogen are a straight or branched saturated alkyl group of 6 to 30 carbon atoms, preferably 10 to 25 carbon atoms , preferably from 12 to 20 carbon atoms, and wherein the other hydrocarbon groups (that is, three when a hydrocarbon group is a long chain hydrocarbon group as mentioned hereinabove, or two when two hydrocarbon groups are groups long chain hydrocarbon as mentioned hereinabove) bonded to the nitrogen, are independently substituted or unsubstituted alkyl chains, linear or branched, of 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and preferably they are methyl groups. The preferred quaternary ammonium compounds for use herein are quaternary ammonium compounds without chlorine / without halogen. Trimethyl quaternary ammonium compounds such as myristyl trimethylsuiphate, cetyl trimethyl sulfate and / or tallow trimethyl sulfate are particularly preferred for use in the compositions of the present invention. Said trimethyl quaternary ammonium compounds are commercially available from Hoechst or Albright & Wilson under the EMPIGEN CM® brand. Among the nonionic surfactants, alkoxylated nonionic surfactants are suitable for use herein. These non-ionic alkoxylated surfactants are preferably alkoxylated alcohols having a carbon chain containing from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms, and most preferably from 10 to 15 carbon atoms. The alkoxylation can be provided by ethoxylate, propoxylate or butoxylate groups, preferably ethoxylate groups. In a preferred aspect, the ethoxylated alcohol comprises from 0.5 to 20, preferably from 2 to 10, preferably from 4 to 6 ethoxy groups. Preferred ethoxylated alcohols are described in Example 1. Blocked alkoxylated nonionic surfactants, which are suitable for use herein, are according to the formula: R1 (O-CH2-CH2) n- (OR2) mO-R3 wherein Ri is a linear or branched C8-C2 alkyl or alkenyl group, an aryl group, an alkaryl group; preferably Ri is a C 8 -C 8 alkyl or alkenyl group, preferably a C 10 -C 15 alkyl or alkenyl group, preferably a C 10 -C 15 alkyl group; wherein R2 is a linear or branched alkyl group of C-1-C10, preferably a linear or branched C2-C10 alkyl group; wherein R3 is a C1-C10 alkyl or alkenyl group, preferably a C1-C5 alkyl group, preferably methyl; and wherein n and m are integers that vary independently on the scale from 1 to 20, preferably from 1 to 10, preferably from 1 to 5; or mixtures thereof. These surfactants are commercially available from BASF under the trademark Plurafac®, from Hoechst under the trademark Genapol®, or from ICI under the trademark Symperonic®. The non-ionic alkoxylated blocked surfactants which are preferred from the above formula are those which are commercially available under the trademark Genapol® L2.5 NR from Hoechst, and Plurafac® from BASF. Particularly preferred surfactants are those selected from the group consisting of alkylsulfate, alkylsulfonate, alkyl ethoxysulfate, alkylbenzenesulfonate, alkylcarboxylate, alkyl ethoxy carboxylate and mixtures thereof. Most preferably, the surfactant system comprises an alkyl sulfonate and an alkyl ethoxy sulfate. Other suitable surfactants include silicone surfactants such as organosilane or organosiloxane. Preferably, the silicone surfactants have a molecular weight of 600 to 10,000, preferably 900 to 6000, preferably about 3000. Such compounds are well known in the art, and examples of them can be found in the US 3 documents. 299 112, US 4 311 695 and US 4 782 095, the disclosures of which are incorporated herein by reference. Suitable siloxane oligomers are described in US 4,005,028. Suitable silicone surfactants include copolymers of polysiloxane and polyethylene glycol, and polydimethylsiloxane copolymers modified with polyalkylene oxide. Other suitable surfactants include fluorinated surfactants comprising a hydrophilic section and a hydrophobic section. The hydrophilic section comprises an alkyl group having from 2 to 12 carbons and a portion of ester, sulfonate or carboxylate. The hydrophobic section is fluorinated. Preferred fluorinated surfactants include alkyl fluorocarboxylates, for example ammonium perfluoroalkylcarboxylate and potassium fluoroalkylcarboxylate. A particularly suitable fluorinated surfactant is an aqueous mixture of potassium fluoroalkylcarboxylate and has from 40 to 44% fluoroalkylcarboxylate of 8 carbon atoms in the alkyl chain, from 1 to 5% fluoroalkylcarboxylate of 6 carbon atoms in the alkyl chain, 1 to 5% fluoroalkylcarboxylate of 4 carbon atoms in the alkyl chain, from 1 to 3% fluoroalkylcarboxylate of 7 carbon atoms in the alkyl chain, and from 0.1 to 1% fluoroalkylcarboxylate of 5 carbon atoms in the alkyl chain . In a preferred aspect of the present invention, the surfactant is a system comprising at least one anionic surfactant, preferably at least two anionic surfactants. Particularly preferred anionic surfactants are linear alkyl or alkylbenzene sulphonate and sulfosuccinate surfactants. More particularly, the preferred anionic surfactants of the surfactant system, when present, are alkylbenzene sulfonates (LAS) and linear C12 dioctylsulfosuccinates. The preferred nonionic surfactant of the surfactant system, when present, is an ethoxylated alcohol having 10 to 14 carbon atoms in the chain and an average of 3 to 8, preferably 3 to 6 ethoxy groups. The ratio of sulfonate surfactant, preferably LAS, to sulfosuccinate surfactant, preferably dioctyl sulfosuccinate, is preferably from 6: 1 to 1: 6, preferably from 5: 1 to 1: 2, preferably from 4: 1 to 1: 1. When the surfactant system comprises a nonionic surfactant, the ratio of sulfonate to sulfosuccinate to nonionic surfactant is preferably 4: 1: 1. Typically, the compositions according to the present invention preferably comprise the surfactant system at a level of from 0.001% to 40%, preferably from 0.001% to 20%, preferably less than 10%, and most preferably from 0.001% to 10% by weight of the composition.

Chelating Agents The compositions of the present invention may comprise a chelating agent as a preferred optional ingredient. Applicants have found that by including a chelating agent in the compositions of the present invention, improved cleaning can be achieved without negatively impacting the action of the surface substantive polymers. Suitable chelating agents can be any of those known to those skilled in the art, such as those selected from the group comprising phosphonate chelating agents, aminocarboxylate chelating agents, other carboxylate chelating agents, polyfunctionally substituted aromatic chelating agents, ethylenediamine- N, N'-disuccinic, or mixtures thereof. The presence of chelating agents contributes to improving the chemical stability of the compositions. Suitable phosphonate chelating agents for use herein may include alkali metal ethane-1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as aminophosphonate compounds, including aminoaminotri (methylene phosphonic acid) (ATMP), nitrilotrimethylene phosphonates (NTP) ), ethylenediaminetetramethylenephosphonates and diethylenetriaminepentamethylenephosphonates (DTPMP). The phosphonate compounds may be present in their acid form or as salts of different cations in some or all of their acid functionalities. Polyfunctionally substituted aromatic chelating agents may also be useful in the present compositions. See, for example, the patent of E.U.A. No. 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelating agent for use herein is ethylenediamine-N, N'-disuccinic acid, or alkali metal or alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. In the patent of E.U.A. No. 4,704,233, November 3, 1987, by Hartman and Perkins, ethylenediamine-N, N'-disuccinic acids, especially the (S, S) isomer are widely described. The ethylene diamine N, N'-disuccinic acids are commercially available, for example, under the brand name ssDSDS® from Palmer Research Laboratories. Suitable aminocarboxylates for use herein include ethylenediaminetetracetates, diethylenetriaminepentacetates (DTPA), N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraminehexacetates, ethanol diglycines, propylenediaminetetraacetic acid (PDTA) and methylglycineadiacetic acid (MGDA), both in their acid form and in their of alkali metal salt, ammonium and substituted ammonium. Particularly suitable aminocarboxylates for use herein are diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid (PDTA), which is commercially available for example from BASF under the brand name Trilon FS® and methylglycineadiacetic acid (MGDA). Additional carboxylate chelating agents to be used herein include salicylic acid, glutamic acid, glycine, malonic acid or mixtures thereof. Another chelating agent to use here is of the formula: wherein Ri, R2, R3 and R4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO2, -C (O) R 'and -SO2R "; where R 'is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl and aryloxy; R "is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy; and R5, Re, R7 and Re are independently selected from the group consisting of -H and alkyl. Particularly preferred chelating agents for use herein are aminoaminotri (methylene phosphonic acid), diethylenetriaminepentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxy-ethanediphosphonate, ethylenediamine-N, N'-disuccinic acid and mixtures thereof. Other chelating agents include polycarboxylates, especially citrate, and complexes of the formula: CH (A) (COOX) -CH (COOX) -0-CH (COOX) -CH (COOX) (B) wherein A is H or OH; B is H or -O-CH (COOX) -CH2 (COOX); and X is H or a salt-forming cation. For example, if in the above general formula A and B are both H, then the compound is oxydisuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartratomonosuccinic acid (TMS) and its water-soluble salts. If A is H and B is -O-CH (COOX) -CH2 (COOX), then the compound is tartrate diuccinic acid (TDS) and its water-soluble salts. Mixtures of these agents are especially preferred for use here. Particularly TMS to TDS are described in the patent of E.U.A. No. 4,663,071, issued for Bush and May 5, 1987.

Other ether polycarboxylates suitable for use herein include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid. Other useful polycarboxylate chelating agents include the etherhydroxypolycarboxylates represented by the structure: HO- [C (R) (COOM) -C (R) (COOM) -O] nH wherein M is hydrogen or a cation, wherein the resulting salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, preferably n averages from about 2 to about 4), and each R is the same or different and is selected from hydrogen, C - ?4 alkyl or substituted alkyl of C1.4 (preferably R is hydrogen). Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in US Patents. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by reference. Among such cyclic compounds, dipicolinic acid and chellanic acid are preferred. Polycarboxylates which are also suitable for use herein are mellitic acid, succinic acid, polymaleic acid, benzene, 1,3,5-tricarboxylic acid, benzene pentacarboxylic acid and carboxymethyloxysuccinic acid, and soluble salts thereof. Carboxylate chelating agents that are also suitable herein include the carboxylated carbohydrates that are described in the U.S.A. No. 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference. Other carboxylates suitable for use herein, but which are less preferred because they do not meet the above criteria, are the alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples of salts of polyacetic acid chelating agents are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine, tetraacetic acid and nitrilotriacetic acid. Other suitable, but less preferred, polycarboxylates are those also known as alkyliminoacetic chelating agents such as methyliminodiacetic acid, alanine diacetic acid, methyl glycine diacetic acid, hydroxypropylene iminodiacetic acid and other chelating agents of alkyliminoacetic acid. Also suitable in the compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in the US patent. No. 4,566,984 of Bush, issued January 28, 1986, incorporated herein by reference. Useful chelating agents of succinic acid include the C5-C20 alkylsuccinic acids and their salts. A particularly preferred compound of this type is dodecenylsuccinic acid. The alkylsuccinic acids are regularly of the general formula R-CH (COOH) CH2 (COOH), ie, succinic acid derivatives, wherein R is hydrocarbon, for example C10-C20 alkyl or alkenyl, preferably C12-C16, or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the aforementioned patents. The succinate chelating agents are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts. Specific examples of succinate chelating agents include: laurylsuccinate, myristylsuccinate, palmitiisuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. Lauryl succinates are the preferred ones of this group, and are described in European patent application 86200690.5 / 0 200 263, published on November 5, 1986. Examples of useful chelating agents also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo -hexanohexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates and copolymers of maleic anhydride with vinylmethyl ether or ethylene. Other suitable polycarboxylates are the polyacetalcarboxylates which are described in the U.S.A. No. 4, 144,226, Crutchfield et al., Issued March 13, 1979, incorporated herein by reference. These polylacetalcarboxylates can be prepared by mixing, under polymerization conditions, a glyoxylic acid ester and a polymerization initiator. The resulting polyacetal carboxylate ester is added to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt and added to a surfactant. Polycarboxylate chelating agents are also described in the U.S.A. No. 3,308,067 to Diehl, issued March 7, 1967, incorporated herein by reference. Said materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Suitable polyphosphonates for use herein are the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates. Most preferably, the chelating agents for use herein are selected from diethylenetriaminepentamethylenephosphonate (DTPMP) or ethane-1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trademark DEQUEST®. Typically, the compositions according to the present invention comprise up to 20%, preferably from 0.01% to 15% by weight, preferably from 0.01% to 10% by weight of the total composition, of a chelating agent.

Enzyme An enzyme or a mixture thereof can be included in the composition of the present invention as an optional ingredient. Preferred enzymatic materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases, conventionally incubated in detergent components or compositions. In the patents of E.U.A. Nos. 3,519,570 and 3,533,139 suitable enzymes are described. Preferred protease enzymes, commercially available, include those sold under the trademarks Alcalase, Savinase, Primase, Durazym and Esperase de Novo Industries A / S (Denmark), those sold under the Maxatase, Maxacal and Maxapem brands by Gist-Brocades, those sold by Genencor International, and those sold under the Opticlean and Optimase brands by Solvay Enzymes . The protease enzyme can be incorporated in the compositions according to the invention at a level of 0.0001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, -amylases obtained from a special strain of B. licheniformis, described in more detail in GB-1, 269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the Rapidase brand of Gist-Brocades, and those sold under the Termamyl, Duramyl and BAN brand of Novo Industries A / S. Very preferred amylases enzymes may be those described in PCT / US 9703635, and in WO 95/26397 and WO 96/23873. The amylase enzyme can be incorporated in the composition according to the invention at a level of 0.0001% to 2% active enzyme by weight of the composition. Lipolytic enzyme may be present at active lipolytic enzyme levels of from 0.0001% to 2% by weight, preferably from 0.001% to 1% by weight, preferably from 0.001% to 0.5% by weight of the compositions. The lipase may be of fungal or bacterial origin, obtained for example from a lipase-producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp., including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipases from mutants of these chemically or genetically modified strains are also useful here. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, and is described in the European patent granted EP-B-0218272. Another preferred lipase here is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus oryza as a host, as described in the European patent application EP-A-0258 068, and which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the Lipolase brand. This lipase is also described in the patent of E.U.A. No. 4,810,414 to Huge-Jensen et al., Issued March 7, 1989.

Hydrotropes The compositions according to the present invention may comprise a hydrotrope as an optional agent. Suitable hydrotropes herein include sulfonated hydrotropes. Any sulfonated hydrotrope known to the person skilled in the art is suitable for use herein. In a preferred embodiment, alkylarylsulfonates or alkylarylsulfonic acids are used. Preferred alkylarylsulfonates include sodium, potassium, calcium and ammonium xylenesulfonates; sodium, potassium, calcium and ammonium toluenesulfonates; sodium, potassium, calcium and ammonium cumenesulfonates; Naphthalene sulfonates of sodium, potassium, calcium and substituted or unsubstituted ammonium; and mixtures thereof. Preferred alkylarylsulfonic acids include xylenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid and mixtures thereof. Preferably, xylenesulfonic acid or p-toluenesulfonate or mixtures thereof are used. Typically, the compositions herein can comprise from 0.01% to 20%, preferably from 0.05% to 10%, and preferably from 0.1% to 5% by weight of the total composition, of a sulphonated hydrotrope. The sulfonated hydrotrope, when present, contributes to the physical and chemical stability of the compositions described herein.

Ions The compositions according to the present invention can additionally comprise a ion, preferably added to the composition in the form of a salt. The preferred ones for use herein are selected from the group consisting of multivalent metal ions. Preferably, said ions are selected from zinc, cadmium, nickel, copper, cobalt, zirconium, chromium, aluminum, iron and / or magnesium. Most preferably, said ions are selected from the metals of group 8 of the periodic table. In the most preferred aspect of the present invention, the composition further comprises a multivalent metal ion selected from the group consisting of aluminum, zinc, copper and iron. For the compositions herein, it is highly preferred to use multivalent metal ions having a valence of more than 2, for example Al + 3, Cu + 3 and / or Fe + 3. Said ions can be added in the form of salts, for example chloride, acetate, sulfate, formate, carbonate and / or nitrate salts, or as a complex metal salt. For example, aluminum may be added in the form of chloride, acetate or aluminum sulfate. Preferably, the aluminum is added to the composition as aluminum chloride. The Applicant has observed that the addition of multivalent metal ions to the compositions described herein has the effect of reducing the viscosity of the composition when applied to a surface, especially the exterior surface of a vehicle. It is believed that this is because the metal ions interact with the polymers described herein as an essential component of the invention, causing the crosslinking of the polymer to form a uniform polymer matrix. When the surfaces are treated with the composition comprising a multivalent metal ion they exhibit improved coverage, unlike the surfaces treated with compositions without the metal ions or only with single-valent metal ions. By the term "cover" is meant herein the extension of a liquid, for example water, to a surface in a sheet-like manner. The improved coverage action provided by the compositions that include metal ions, results in further reduction of watermarks, blotches or spots. Typically, said ions may be present at a level of up to 20%, preferably from 0.0001% to 10% by weight of the total composition.

Foaming controlling agents The compositions according to the present invention may further comprise a foam controlling agent such as 2-alkylalcanol, or mixtures of several of them, as a preferred optional ingredient. Particularly suitable for use herein are 2-alkylalkanols having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12, and a terminal hydroxy group, said alkyl chain being substituted at the position with an alkyl chain which it comprises from 1 to 10 carbon atoms, preferably from 2 to 8, and preferably from 3 to 6.

Such suitable compounds are commercially available, for example, in the Isofoi® series, such as Isofol® 12 (2-butyloctanol) or Isofol® 16 (2-hexyldecanol). Other foam controlling agents may include alkali metal fatty acids (eg sodium or potassium), or soaps thereof, containing from about 8 to about 24, preferably from about 10 to about 20, carbon atoms. Fatty acids, including those used in the preparation of soaps, can be obtained from natural sources such as for example glycerides derived from plants or animals (for example palm oil, coconut oil, Brazilian palm oil, soybean oil, castor oil, tallow, whale oil, fish oil, fat, butter and mixtures thereof). The fatty acids can also be prepared synthetically (for example by oxidation of petroleum materials or by the Fischer-Tropsch process). Alkali metal soaps can be made by direct saponification of fats and oils or by neutralization of the free fatty acids that are prepared in a separate manufacturing process. The sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow are particularly useful, that is, soaps of tallow and coconut of potassium. The term "tallow" is used herein with respect to mixtures of fatty acids typically having an approximate distribution of carbon chain length of 2.5% C14, 29% C16, 23% C18, 2% palmitoleic, 41.5% oleic and 3% linoleic (the first three fatty acids mentioned are saturated). Also included within the term tallow other mixtures with similar distribution, such as fatty acids derived from various tallow and animal lard. The tallow may also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated fatty acid portions to saturated fatty acid portions. When used herein the term "coco" refers to mixtures of fatty acids typically having an approximate carbon chain length distribution of 8% C8, 7% C10, 48% C12, 17% C14, 9% C16, 2 % C18, 7% oleic and 2% linoleic (the first six fatty acids mentioned are saturated). Other sources having similar carbon chain length distribution, such as palm kernel oil and Brazilian palm oil, are also included with the term "coconut oil". A preferred silicone foam controller agent is described by Bartoilota et al., In the U.S. patent. No. 3,933,672. Other particularly useful foam controlling agents are self-emulsifying silicone foam controlling agents, which are described in the German patent application DTOS 2 646 126, published on April 28, 1977. An example of such compounds is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred silicone foam controlling agents are described in the co-pending European patent application No. 92201649. 8. Said compositions may comprise a silicone / silica mixture in combination with non-porous fumed silica, such as Aerosil®. An especially preferred foam controlling agent is the foam controller system comprising a mixture of silicone oils and 2-alkylalkanols. Typically, the compositions herein may comprise up to 4% by weight of the total composition, of a foam controlling agent or of a mixture thereof, preferably from 0.1% to 1.5%, and most preferably from 0.1% to 0.8% .

Solvents The compositions of the present invention may optionally comprise a solvent or a mixture of solvents. It has been found that the solvent improves the runoff of water on a surface. Solvents for use herein include all those known to those skilled in the art. Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and preferably from 8 to 10 carbon atoms; glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, C -? - C5 alkoxylated linear alcohols, C1-C5 linear alcohols, C8-C alkyl and cycloalkyl hydrocarbons and halohydrocarbons? 4, C 1 -C 16 glycol ethers, and mixtures thereof.

Suitable glycols for use herein correspond to the formula HO-CR1 R2-OH, wherein R1 and R2 are independently H or an aliphatic, saturated or unsaturated, and / or cyclic C2-C? 0 hydrocarbon chain. The glycols suitable for use herein are dodecane glycol and / or propanediol. Suitable alkoxylated glycols for use herein correspond to the formula R- (A) n-R 1 -OH, wherein R is H, OH, a saturated or unsaturated linear alkyl of 1 to 20 carbon atoms, preferably 2 to 15, and preferably from 2 to 10, wherein R1 is H or a saturated or unsaturated linear alkyl of 1 to 20 carbon atoms, preferably 2 to 15, and preferably 2 to 10; and A is an alkoxy, preferably ethoxy, methoxy and / or propoxy group, and n is from 1 to 5, preferably 1 to 2. The alkoxylated glycols suitable for use herein are methoxyoctadecanol and / or ethoxyethoxyethanol. Alkoxylated aromatic alcohols which are suitable for use herein correspond to the formula R (A) n-OH, wherein R is an aryl group substituted with alkyl or unsubstituted with alkyl, having from 1 to 20 carbon atoms, preferably from 2 to 15, and preferably from 2 to 10, wherein A is an alkoxy, preferably butoxy, propoxy and / or ethoxy group, and n is an integer from 1 to 5, preferably from 1 to 2. Suitable alkoxylated aromatic alcohols they are benzoxyethanol and / or benzoxypropanol. Aromatic alcohols suitable for use herein correspond to the formula R-OH, wherein R is an aryl group substituted with alkyl or unsubstituted with alkyl, having from 1 to 20 carbon atoms, preferably from 1 to 15, and preferably from 1 to 10. For example, an aromatic alcohol suitable for use herein is benzyl alcohol. Branched aliphatic alcohols which are suitable for use herein correspond to the formula R-OH, wherein R is a branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, preferably 2 to 15, and preferably from 5 to 12. Branched aliphatic alcohols particularly suitable for use herein include 2-ethylbutanol and / or 2-methyl butanol. Branched and alkoxylated aliphatic alcohols, which are suitable for use herein, correspond to the formula R (A) n-OH, wherein R is a branched, saturated or unsaturated alkyl group, of 1 to 20 carbon atoms, preferably 2 to 15, and preferably from 5 to 12, wherein A is an alkoxy, preferably butoxy, propoxy, and / or ethoxy group, and n is an integer from 1 to 5, preferably from 1 to 2. The alkoxylated branched aliphatic alcohols which are Suitable include 1-methylpropoxyethane and / or 2-methylbutoxyethanol. Alkoxylated C1-C5 linear alcohols which are suitable for use in the present, correspond to the formula R (A) n-OH, wherein R is a linear, saturated or unsaturated alkyl group, of 1 to 5 carbon atoms, preferably 2 to 4, wherein A is an alkoxy group, preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2. Alkoxylated linear aliphatic alcohols of C 1 -C 5 which are suitable, are butoxypropoxypropanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxipropoxypropanol is commercially available under the n-BPP® brand from Dow Chemical. Suitable C1-C5 linear alcohols that can be used herein correspond to the formula R-OH, where R is a linear, saturated or unsaturated alkyl group of 1 to 5 carbon atoms, preferably 2 to 4.

Suitable linear C1-C5 alcohols are methanol, ethanol, propanol, or mixtures thereof. Other suitable solvents include diglycol butyl ether (BDGE), triglycol butyl ether, ter-amyl alcohol and the like. Particularly preferred solvents that can be used herein are butoxypropoxypropanol, diglycol butyl ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol, and mixtures thereof. Other suitable solvents include mineral spirits, preferably the mineral spirit commonly known as the white spirit. In one embodiment, particularly preferred solvents are selected from linear or branched C1.5 alkyl solvents, for example linear or branched C1.5 alcohols. Particularly preferred solvents for use in this embodiment are ethanol and / or isopropanol. Typically, the compositions of the present invention, when essentially aqueous, comprise up to 30% by weight of the total composition, of a solvent or mixtures of solvents, preferably up to 10% by weight, and preferably up to 8%.

However, when the composition is essentially non-aqueous as described below, the composition may preferably comprise from 60% to 99.5%, preferably from 70% to 99%, preferably from 90% to 99%, and preferably from 95%. % to 99% by weight of the total composition, of a solvent or mixtures of solvents.

PH buffers In the preferred embodiment of the present invention, the compositions are preferably formulated on a neutral pH scale, typically 4.0 to 9.0, most preferably 4.5 to 9.5. The compositions according to the present invention may further comprise a pH buffer or a mixture of several thereof, that is, a system composed of a compound or a combination of compounds whose pH changes only slightly when an acid is added or a strong base. PH buffers suitable for use herein under neutral to basic conditions include borate, phosphonate, silicate buffers and mixtures thereof. Suitable borate buffers for use herein include alkali metal salts of borates and alkylborates, and mixtures thereof. Suitable borate buffers for use herein are the alkali metal salts of borate, metaborate, tetraborate, octaborate, pentaborate, dodecaborate, borotrifluoride and / or aiquilborate containing from 1 to 12 carbon atoms, and preferably from 1 to 4. suitable alkylborates include methylborate, ethylborate and propylborate. Particularly preferred herein are the alkali metal salts of metaborate (e.g., sodium metaborate), tetraborate (e.g., sodium tetraborate decahydrate), or mixtures thereof. Boron salts such as sodium metaborate and sodium tetraborate are commercially available from Bórax and Societa Chimica Larderello under the trade names sodium metaborate® and Bórax®. Suitable pH buffers for use herein under acidic conditions include organic acids and mixtures thereof. Organic acids suitable for use herein include monocarboxylic acids, dicarboxylic acids and tricarboxylic acids, or mixtures thereof. Preferred organic acids for use herein include acetic acid, citric acid, malonic acid, maleic acid, malic acid, lactic acid, glutaric acid, glutamic acid, aspartic acid, methylsuccinic acid, succinic acid, or mixtures thereof. Particular preference is given here to citric acid and succinic acid or mixtures thereof. Citric acid is commercially available as an aqueous solution of Jungbunzlauer under the trade name Citric acid®. Typically, the compositions according to the present invention may comprise up to 15% by weight of the total composition, of a buffer, or mixtures of several of them, preferably from 0.001% to 10%, preferably from 0.001% to 5%. %, and most preferably from 0.005% to 3%.

Thickening Agent The composition of the present invention may preferably comprise a thickening agent. A thickening agent is an ingredient that is specifically added to the composition of the present invention to increase the viscosity of the composition. Suitable thickeners are those known in the art. Examples include gum-type polymers (for example xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and its derivatives and polycarboxylate polymers. In a particularly preferred embodiment of the present invention, the thickening agent comprises a gum-type polymer or a polycarboxylate polymer. Particularly preferred examples of these thickening agents are xanthan gum and interlaced polycarboxylate polymer, respectively. The gum-like polymer can be selected from the group consisting of polysaccharide hydrocolloids, xanthan gum, guar gum, succinoglycan gum, cellulose, derivatives of any of the foregoing and mixtures thereof. In a preferred aspect of the present invention, the gum-type polymer is a xanthan gum or a derivative thereof. The polycarboxylate polymer can be a homo- or copolymer of monomer units selected from acrylic acid, methacrylic acid, maleic acid, malic acid, maleic anhydride. Preferred polycarboxylate polymers are carbopol from BF Goodrich. Suitable polymers have a molecular weight in the range of 10,000 to 100,000,000, preferably 1,000,000 to 10,000,000.

Radical scavengers The compositions of the present invention may comprise a radical scavenger or a mixture of several thereof. Suitable radical scavengers for use herein include the well-known substituted mono- and dihydroxybenzenes and their analogs, alkyl and arylcarboxylates and mixtures thereof. Radical scavengers Preferred of these for use herein include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, tert-butyl-hydroxyanisole, benzoic acid, toluic acid, catechol, t -butilcatecol, benzylamine, 1, 1, 3-tris (2-methyl-4-hydroxy-5-t-but¡lfen¡l) butane, n-propyl gallate, or mixtures thereof, and most preferred di-ter -butylhydroxytoluene. Radical scavengers such as N-propylgalate may be commercially available from Nipa Laboratories under the trademark Nipanox S1®. When radical scavengers are used, they are typically present herein in amounts of up to 10% by weight of the total composition, and preferably from 0.001% to 0.5% by weight.

Dirt suspension polymer The compositions according to the present invention may further comprise a soil suspension polymer, for example a polyamine soil suspension polymer or mixtures thereof, as an optional ingredient. Any polyamine soil suspension polymer known to those skilled in the art can be used here. Particularly suitable polyamine polymers for use herein are polyalkoxylated polyamines. These materials can be conveniently represented as molecules of the empirical structures with repeating units: [N R], Amine form (alkoxy) R1 IN RI. nX "Quaternized form (alkoxy) wherein R is a hydrocarbyl group, usually from 2 to 6 carbon atoms; R1 may be a C1-C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy and the like, and "and" is from 2 to 30, preferably 10-20; n is an integer of at least 2, preferably 2-20, preferably 3-5; and X "is a tai anion such as halide or metiisulfato, originating from the quaternization reaction. The polyamines highly preferred for use herein are polyethyleneamines called ethoxylated, ie, the polymerized reaction product of ethylene oxide with ethyleneimine, has the general formula: when y = 2-30. For use herein, an ethoxylated polyethyleneamine, in particular ethoxylated tetraethylenepentamine, and quaternized ethoxylated hexamethylenediamine are particularly preferred.

Perfumes Perfumes suitable for use herein include materials that provide an olfactory aesthetic benefit and / or cover any "chemical" odor that the product may have. The main function of a small fraction of the very volatile, low boiling perfume components (which have low boiling points) is to improve the odor of the product itself, rather than to have an impact on the subsequent odor of the product. the surface to be cleaned. However, some of the less volatile, high-boiling perfume ingredients provide a fresh and clean impression to the surfaces, and it is desirable that these ingredients are deposited and are present on the dry surface. The perfume ingredients can be easily solubilized in the compositions, for example by means of the amphoteric surfactant. The ingredients and perfume compositions suitable for use herein are those conventional known in the art. The selection of any perfume component, or the amount of perfume, is based solely on aesthetic considerations.

Suitable perfume compositions and compositions can be found in the art, including US Patents. Nos. 4,145,184, by Brain and Cummins, issued March 20, 1979; 4,209,417, by Whyte, issued June 24, 1980; 4,515,705, by Moeddel, issued May 7, 1985; and 4,152,272, de Young, issued May 1, 1979; All of these patents are incorporated herein by reference. In general, the degree of substantivity of a perfume is approximately proportional to the percentages of the substantive perfume material used. Relatively substantive perfumes contain at least about 1%, preferably at least about 10%, of substantive perfume materials. Substantive perfume materials are those odorant compounds that are deposited on surfaces by the cleaning operation and are detectable by people with normal olfactory acuity. Such materials typically have lower vapor pressures than the average perfume material. Also typically, they have molecular weights of about 200 and higher, and are detectable at levels below those of the average perfume material. The perfume ingredients useful herein, along with their odor character, and their physical and chemical properties such as boiling point and molecular weight, are given in "Perfume and Flavor Chemicals (Aroma Chemicals)", Steffen Arctander, published by the author, 1969, incorporated herein by reference. Examples of highly volatile low boiling perfume ingredients are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, isopropyl acetate, camphene, cis-citral (neral), citronellal, citronellol, citronellyl acetate, para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethylphenylcarblnol, eucalyptol, geranial, geraniol, geranyl acetate, geranylnitrile, cis-3-hexenyl acetate, hydroxycitroneal, d-limonene, linalool, linalool oxide, linalyl acetate, propionate, linalyl, methyl anthranilate, alpha-methyl-ionone, methylnon-acetaldehyde, methylphenylcarbinyl acetate, levo-menthyl acetate, menthone, iso-menthone, myrcene, myrcenyl acetate, mircenol, nerol, neryl acetate, nonyl acetate, phenylethyl alcohol , alpha-pinene, beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, terpinyl acetate and vertenex (para-tert-butylcyclohexyl acetate). Some natural oils also contain large percentages of highly volatile perfume ingredients. For example, bleach contains as main components: linalool, linalyl acetate, geraniol and citronellol. Lemon oil and orange terpenes contain both approximately 95% d-limonene. Examples of moderately volatile perfume ingredients are: amylcinnamic aldehyde, soamily salicylate, beta-caryophyllene, cedrene, cinnamic alcohol, coumarin, dimethylbenzylcarbinyl acetate, ethylvanillin, eugenol, iso-eugenol, flower-acetate, heliotropin, 3-cis-hexenyl salicylate, hexyl salicylate, lilial (para-tert-butyl aldehyde -alpha-methylhydrocinnamic acid), gamma-methylionone, nerolidol, patchouli alcohol, phenylhexanol, beta-selinose, trichloromethylphenylcarbinyl acetate, triethyl citrate, vanillin and veratraldehyde. The cedar wood terpenes are mainly composed of alpha-cedrene, beta-cedrene and other sesquiterpenes from CldH2 - Examples of less volatile high-boiling perfume ingredients are: benzophenone, benzyl salicylate, ethylene brasylate, galaxolide (1, 3,4,6, 7,8-hexahydro-4,6,6,7, 8,8-hexamethyl-cyclopenta-gamma-2-benzopyran), hexyl cinnamic aldehyde, lyral (4- (4-hydroxy-4-methyl-pentyl) -3-cyclohexen-10-carboxaldehyde), methyl cedrylon, methyl dihydrojasmonate , methyl-beta-naphthyl ketone, moss indanone, moss ketone, moss tibetan and phenylethylphenyl acetate. The selection of any particular perfume ingredient is dictated primarily by aesthetic considerations. The compositions herein may comprise a perfume ingredient, or mixtures thereof, in amounts of up to 5.0% by weight of the total composition, preferably in amounts of 0.0005% to 1.5%.

Secondary ingredients Dyestuffs including dyes and well-known pigments can be added to the composition in minor amounts. Other preferred components, although secondary, include preservatives. By "preservative" is meant any compound that can be stably added to the composition and that destroys or at least inactivates microbes, for example bacteria and fungi. Any suitable preservative currently available in the market may be incorporated herein; see, for example, those described in the HAPPI journal of the May 1999 edition p. 78-94. Particularly preferred preservatives are phenoxyethanol, available for example from BASF under the trademark Protectol PP, or glutaraldehyde, available for example from BASF under the Protectol GDA trademark.

Form of the Composition The compositions of the present invention may be in any form, for example, in liquid, gel, foam, particles or tablets. When the composition of the present invention is a liquid, it can be aqueous or non-aqueous, diluted or concentrated. When the composition is aqueous, it preferably comprises from 1% to 99.9% of water, preferably from 50% to 99.8%, preferably from 80% to 99.7% of water. As mentioned, it is alternatively contemplated that the composition may be non-aqueous. By "non-aqueous" it is meant that the composition is substantially free of water. More precisely, it is understood that the compositions do not contain water expressly added, and therefore the only water that is present in the composition is water of crystallization, for example in combination with a raw material.

Form of packaging of the compositions The compositions herein can be packaged in a variety of packages known to those skilled in the art, depending on the form of the composition. The liquid compositions are preferably packaged in conventional bottles that do not react chemically with the composition they store. Preferably, the bottles are made of plastic. In a particularly preferred embodiment, the composition can be packaged in spray dispensing containers. Such containers are usually made of plastic materials of synthetic organic polymers. The spray device of the container can be operated manually or electrically. Manually operated spray devices include trigger operated spray dispenser or pump operated spray dispenser. Spray dispensers suitable for use in accordance with the present invention include manually operated trigger-type foam dispensers, sold for example by Specialty Packing Products, Inc. or by Continental Sprayers, Inc. These types of dispensers are described for example in the US patent No. 4,701, 311 of Dunning and others and in the patents of E.U.A. Nos. 4,646,973 and 4,538,745, both for Focarracci. For use here, spray type dispensers such as the T 8500® commercially available from Continental Spray International, or T 8100®, commercially available from Canyon, Northern Ireland, are particularly preferred. In said dispenser, the liquid composition is divided into fine liquid droplets that form a spray that is directed on the surface to be treated. In fact, in said spray-type dispenser the composition contained in the body thereof is directed through the head of the dispenser by energy communicated to a pumping mechanism by the user, as said user activates said pumping mechanism. More particularly, in said spray-type dispenser head, the composition is forced against an obstacle, for example a grid or a cone or the like, thus providing shocks to help atomize the liquid composition, that is, to assist in the formation of a liquid. liquid droplets Alternatively, the composition can be packaged in an electrically operated spray device, in which a source of electricity is used to drive the spray. In another preferred embodiment of the present invention, a liquid composition according to the present invention is applied to the surface using a dispensing device, preferably a spray dispenser. Said spray dispenser is a container having at least one opening through which said composition is dispensed to produce a spray of droplets. Said spray dispenser may comprise means for supplying the composition by means of a pump ("pump spray dispenser"), or it may be operated by any source of pressurized gas, such as an aerosol can or a pressurizer. Pump spray dispensers can be operated manually or electrically. Said dispensers are particularly preferred for treating a large area, and / or for applying a high amount of product on a very stained surface, since they facilitate the use for the consumer. Said spray dispensers ensure that a high amount of product is applied on said highly stained surface, as well as a uniform coverage of the area to be treated. The preferred spray dispensers here are the electrically operated spray dispensers. A preferred spray dispenser is a container wherein the supply means of the composition comprises an electrically driven pump and a spray arm. Said spray arm is extended or extendable and has at least one opening so that, during operation, the composition is pumped by said electrically driven pump from the container, through the spray arm, to the opening from which it is dispensed. . It is preferred that the spray arm communicates with the container by means of a flexible connector. The spray arm may have at least one opening located along its length. The spray arm makes it easier to control where the composition is sprayed and, therefore, increases the accuracy with which the composition is applied. The electrically driven pump can be, for example, a gear pump, a propeller pump, a piston pump, a propeller pump, a peristaltic pump, a diaphragm pump, or any other miniature pump. In a most preferred embodiment of the electrically driven pump for use herein, the pump is a gear pump with a typical speed between 6000 rpm and 12000 rpm. The electrically driven pump is driven by means such as an electric motor that typically produces a torque of between 1 and 20 mN.m. The electric motor in turn must be provided with a power source. The power source can be electricity from the main line (optionally by transformer), or it can be a disposable battery or a rechargeable battery. The spray arm may be rigidly extended. However, said spray arm can be difficult to store and preferably the spray arm is extendable by means of telescopic or folding configuration.

The cleaning process The present invention also encompasses a method for cleaning a surface, for example an exterior surface of a vehicle, for example a car; wherein the surface to be cleaned is contacted with the composition of the present invention. By surfaces is meant any type of surface typically found in houses, such as kitchens, bathrooms, or exterior surfaces of a vehicle, for example floors, walls, tiles, windows, sinks, showers, plasticized shower curtains, toilets, toilets, dishes, accessories and furniture and the like, made of different materials such as ceramics, vinyl, non-waxy vinyl, linoleum, melamine, glass, any plastic, laminated wood, metal, especially steel and chrome, or any painted, varnished or sealed surface and the like . Surfaces also include household appliances that include, without limitation, refrigerators, freezers, washing machines, dryers, ovens, microwave ovens, dishwashers, and so on. The present composition is especially effective in cleaning ceramics, steel, plastic, glass and the painted exterior surface or with another type of finish of a vehicle, for example a car. Optionally, the cleaning composition is applied to the surface after a pre-rinse step. The composition can be applied using a cloth or sponge on which the composition is applied, or by emptying the composition on the surface. Alternatively, the composition can be applied by spraying it onto the surface, using a spray dispenser such as those described above. Once the composition has been applied to the surface, it can optionally be rinsed, usually with water, and allowed to dry naturally. Optionally, the user can wait between the application and the rinsing of the composition, to leave it at a maximum working time. A particular benefit of the present composition is that the surface can be cleaned as described above and allowed to dry naturally, without the formation of water spots or streaks.

EXAMPLES The present invention will be further illustrated by the following examples. All levels are expressed in percent by weight of the total composition.

EXAMPLE 1 EXAMPLE 1 (Continued) SSP is a polyethyleneamine of PM 3000 propoxylated to one degree and ethoxylated to a degree of 27.

EXAMPLE 2 PVPVl is N-vinylimidazole-N-vinylpyrrolidone, provided by BASF under the trademark Luvitec VP155K18P. PVNO is N-oxide of polyvinylpyridine, provided by Reilly, which has molecular weight.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. - A cleaning composition suitable for cleaning a surface, comprising a substantive surface polymer, wherein said polymer is capable of modifying the surface to make it hydrophilic, providing a contact angle between the water and the surface of less than 50 °.

2. A cleaning composition suitable for cleaning a surface, comprising a substantive surface polymer, wherein said polymer is capable of lastingly modifying the surface to make it hydrophilic, providing a contact angle between the water and the surface of less than 50. °.

3. The cleaning composition according to the preceding claim, further characterized in that said polymer is able to adhere to the surface during at least one rinse, determined according to the rinsing test method described herein.

4. The cleaning composition according to the preceding claim, further characterized in that said polymer is able to adhere to the surface during at least five rinses, determined in accordance with the rinsing test method described herein.

5. The cleaning composition according to the preceding claim, wherein the surface is ceramic, enamel, vinyl, non-waxy vinyl, linoleum, melamine, glass, any plastic, laminated wood, metal, especially chrome, varnished or sealed surfaces , and the exterior surfaces of a vehicle.

6. The cleaning composition according to claim 5, wherein the surface is an exterior surface of a vehicle.

7. The cleaning composition according to any of the preceding claims, further characterized in that the polymer comprises at least a hydrophobic or cationic portion and at least a hydrophilic portion.

8. The cleaning composition according to any of the preceding claims, further characterized in that the polymer is present at a level of 0.001% to 10% by weight of the composition.

9. The cleaning composition according to any of the preceding claims, further characterized in that the polymer is selected from the group consisting of polymers of N-vinylimidazole-N-vinylpyrrolidone (PVPVl), polymers of N-oxide polyvinylpyridine (PVNO) , quaternized vinylpyrrolidone / acrylate or dialkylaminoalkyl methacrylate copolymers, or mixtures thereof.

10. - The cleaning composition according to any of the preceding claims, further characterized in that it comprises a surfactant or a system of surfactants.

11. The cleaning composition according to any of the preceding claims, further characterized in that it comprises a chelant.

12. The cleaning composition according to any of the preceding claims, further characterized in that it comprises a solvent, preferably a C1-5 alcohol.

13. The cleaning composition according to any of the preceding claims, further characterized in that it comprises a soil removal polymer.

14. The cleaning composition according to any of the preceding claims, further characterized in that it comprises a ivalent metal ion and salts thereof.

15. The cleaning composition according to claim 14, further characterized in that the ivalent metal ion is selected from the group consisting of Al + 3, Zn + 2, Cu + 2, Cu + 3, Fe + 2, Fe + 3, salts thereof, and mixtures thereof.

16. A method for cleaning a surface, comprising optionally pre-rinsing the surface, applying to the surface the composition claimed in any of claims 1 to 13, and allowing to dry naturally.

17. - The method according to claim 14, further characterized in that the surface is rinsed before the surface is allowed to dry naturally.

18. The method according to claim 14 or 15, further characterized in that the composition is applied to the surface using a spray device.

19. The use of a composition as claimed in any of claims 1 to 13, to clean the exterior surface of a vehicle.

20. The use of a composition as claimed in any of claims 1 to 13, for cleaning ceramics, plastic and metal. íe